4-Chloro-2-iodoaniline

Pale brown to purple low melting solid

General procedure: To a solution of the aniline (1, 20.0 mmol) in a mixture of H2O (100 mL) and MeOH(300 mL), was added conc. hydrochloric acid was added until pH was 1–2 (pH strip).Then an aqueous solution of NaICl2 (50percent w/w 1.1–4;.8 molar equiv; for amount, seeTable) was added dropwise and the resulting mixture was stirred with a stirring bar atroom temperature for 3–4 h. Saturated aqueous NaHSO3 was added until negative starchtest was obtained and the product was worked up.When no precipitate was clearly visible in the product mixture, the mixture was madeslightly basic (pH strip) by dropwise addition of an aqueous solution of NaOH (1 M) andextracted with Et2O. The combined organic phases were dried (MgSO4), filtered, and concentratedunder vacuum to give a solid.When a visible precipitate was obtained, the solid was isolated by gravity filtration(each case specified below) and the filtrate was then made slightly basic (pH strip) byaddition of an aqueous solution of NaOH (1 M) and extracted with Et2O. The combinedorganic extracts were dried (MgSO4), filtered, and concentrated under vacuum to afford asolid.All the solids were analysed by TLC (silica gel; varying mixtures of hexanes/ethylacetate). When a solid consisted of several products, the compounds were separated andpurified by flash chromatography (silica gel; hexanes/ethyl acetate 9:1 when not otherwisestated).The products obtained were characterized by mps (and comparison with lit. mps), IR, MS, 1H- and 13C-NMR spectra as well as elemental analysis for all new compounds. Theanisidines gave no products that could be characterized. Anilines 1a–1j gave products assummarized below; most of them are known from the literature.General procedure: To a stirred solution of the substrate (1 mmol) in CHGeneral procedure: To a solution of aromatic compound (10 mmol) in acetonitrile (5 mL) in a 100 mL round-bottomed flask with a magnetic bar was added choline chloride(10 mmol), potassium peroxodisulfate (10 mmol) and iodine (15 mmol). The reaction mixture was stirred for the appropriate time at 65 °C. The progress of the reaction was monitored by TLC. The reaction mixture was poured into aqueous sodium thiosulfate solution (1 mol/L) in order to remove unreacted iodine and extracted with ethyl acetoacetate (10 mL, 3 times). Organic layer is dried over anhydrous sodium sulphate. Evaporation of the solvent under vacuum followed by column chromatography on silica gel gave the corresponding iodinated compounds (Scheme-I).General procedure: A mixture of aromatic/heteroaromatic amine (1 mmol) and 1-butyl-3-methylpyridinium dichloroiodate (BMPDCI) (1.2 mmol) was heated to 80°C for 1-4 h. After completion of the reaction (monitored by TLC), ethyl acetate was added, followed by addition of water. The organic layer was separated and the aqueous layer was extracted three times with ethyl acetate. The combined organic layer was dried using sodium sulfate and evaporated under vacuum to afford the crude product, which on further column chromatography using silica gel afforded the pure iodinated product as shown in Table 1.General procedure: General procedure for the iodination of aryl amines under solvent-free conditions.DBDABCODCI (0.5 mmol) and aryl amine (1 mmol) were triturated together in a porcelainmortar at room temperature. After completing reaction which monitored by TLC, the ethylacetate added to mixture and filtered, the organic layer washed with 5percent aqueous sodiumthiosulfate, and dried over MgSO4. The solvent was removed in vacuum and the crude mixturewas purified by column chromatography using ethyl acetate and hexane mixture and analyzedby m.p. and 1H NMR spectroscopy.A typical procedure was followed for one-pot synthesis of substituted 2-iodoaniline and 2-iodoacetanilide from substituted aniline. A mixture of 5 g of substituted aniline 1–6 shown inTable 1, granulated iodine (1 mol. equiv.) and copper(II) acetate(1 mol. equiv.) were stirred in 50 mL of glacial acetic for 30 min.The reaction mixture was refluxed for 12 h with constant stirring at 120 C. Then the reaction mixture was allowed to cool at room temperature. The precipitate of copper(I) iodide was removed byfiltration and the filtrate was poured into water and extracted with chloroform (3 50 mL). The combined chloroform extracts were washed with sodium hydrogen carbonate solution, sodium thiosulfate solution, distilled water and dried with anhydrous sodium sulfate.A crude semi-solid mass was obtained after removal of solvent. The crude product was purified by column chromatographyon silica gel using n-hexane/ethyl acetate as eluant (4:1) and compounds 7–24 were isolated.

Molecular Weight:253.47
XLogP3:2.5
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:1
Exact Mass:252.91552
Monoisotopic Mass:252.91552
Topological Polar Surface Area:26
Heavy Atom Count:9
Complexity:99.1
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes